Cyanoacetyl coupler



'sification are:

Patented Mar. 9, 1943 CYANOACETYL COUPLER I Charles F. H. Allen and PaulW. Vittum, Rochester, N. Y., assignors to Eastman Kodak Company,Rochester, N. Y., a corporation of New Jersey N Drawing. ApplicationDecember 23, 1940, Se-

rial No.'371,396. In Great Britain January 2,

21 Claims.

This invention relates to photography and more particularly to compoundswhich form dyes by coupling with the developing compound on development.

The method of forming colored photographic images by depositing acolored compound in the photographic layer adjacent to the silver imagehas been described in numerous prior patents. The present inventionrelates to a process in which the color-forming compound is containedpreferably in the developing solution, but might also be in thesensitive material, and forms a dye concurrently in the region adjacentto silver formed on development of the silver image by coupling; withthe oxidation product of the photographic developer. In U. S. Patent No.2,115,394, granted April 26, 1938, to Mannes, Godowsky and Peterson,there are disclosed cyanoacetyl compounds useful as coupler com-- poundsin photographic developers. In U. S.

Patents Nos. 2,113,330; granted April 5, 1938 m Mannes and Godowsky, and2,108,602, granted February 15, 1938, -to Mannes and Godowsky, othercyanoacetyl compounds are disclosed.

We have found that there are certain cyanoacetyl coupler compounds whichhave better (5) ciHi Cn zs These compounds, according to their molecularsize and solubility, maybe incorporated either in photographic emulsionsor indeveloping soluphotographic characteristics than those which havehithertobeen known. These new, cyanoacetyl couplers which we describehave sharper absorption bands and considerably higher transmissions in-aregion of the spectrum such as the blue, with the result thatsatisfactory colors for subtractive color processes are obtained uponcoupler development.

The compounds which we contemplate using have the general formula:

Where X is a.CN or COOR: group, R3 is alkyl,

Z is NHRi or alkoxy, Ri'and R2 are H, alkyl or aryl, Y is oxygen, sulfuror NR4, where R4 is H,

alkyl, or aryl.

Compounds which fall under this general clas- Cyanoacetyl urea (2) NEH-O0-NH-0 O-CH2C 0 0 0 2H: I Ethyl malonyl urea a Nnr-o-NH-c 0-o Ha-CNOyanoacetyl guanidine (4) 04m NH-C ONH-C O-CHi-GN Butyl eyanoacetyl ureations. Usually the less highly N substituted compounds (those compoundshaving substituents of lower molecular weight) are used in developers.

Compounds 1-5 and 7-9 are suitable for use in a developing solution andcompound 6. may be incorporated into an emulsion layer. These couplersmust contain a coupling function, which is in this case a reactivemethylene group. By

coupling function" we mean afunctional or reactive group commori tocoupler compounds which react with primary aromatic amino developers. Byreactive methylene we mean aCH z group which is reactive in the couplingprocess. The reactive methylene group is present between two negativecenters as in the groups CO- CH2- CO- or COCH2CN. One of the atoms ofthe methylene group may, in general be substituted without destroyingthe chem ical activity of the group, if the substituentis one which issplit off easilysuch as halogen or carboxyl.

The aromatic amino developing agents used with the coupler compounds ofour,invention include the mono-, di-, and tri-aminoaryl com-- pounds andtheir derivatives formed by substitution in the amino group as well asin the ring, such as alkylphenylenediamines and alkyltoluenediamiries.These compounds are usually used in the salt form, such as thehydrochloride or the sulfate, which are more stable than the aminesthemselves. Suitable compounds are diethyl-p-phenylenediaminehydrochloride, monomethyl-p-phenylenediamine hydrochloride,dimethyl-p-phenylenediamine hydrochloride and dimethyl pphenylenediamine sulfate.

may also be used where the amino group is unsubstituted. All of thesecompounds have an unsubstituted amino group which enables oxida-Thep-aminophenols and their substitution products I color formingcompounds to form a dye image.

- where R is alkyl, and R1 and R2 are selected from the group consistingof H, alkyl and aryl, Y

The following developer formula may be used with the compounds of ourinvention:

A. p-Aminodiethyl aniline sulfate grams 2 Sodium sulfite anhydrous do 5Sodium carbonate anhydrous do 20 Potassium bromide do 2 Water to"liter..- 1

B. Coupler grams 1-5 Solvent (acetone or isopropyl alcohol) cc 100 Add Bto A.

Our development process may be employed for the production of coloredphotographic images in layers of gelatin or other carrier such ascollodion, organic esters of cellulose or synthetic resins. The supportfor the emulsion may be a transparent material such as glass, acellulose ester, or an opaque material such as paper or an opaquecellulose ester. The superimposed layers may be sensitized to recorddifferent regions of the spectrum.

The cyanoacetyl couplers which we use are, in general, prepared by theinteraction of cyanoacetic acid and ureas, guanidines, cyanamide orurethane in the presence of a dehydrating agent such as phosphorousoxychloride or acetic anhydride in a manner similar to that described inthe German, Patents Nos. 175,415 and 115,253. The-malonyl urea couplersare prepared by the interaction of an acid chloride of malonic ester anda urea, thiourea, guanidine, etc. as described in the German Patent No.193,447.

The methods and compounds set forth in the present specification areillustrative only and it is to be understood that our invention islimited only by the scope of the appended claims.

We claim:

1. A color forming photographic developer comprising an aromatic aminodeveloping compound containing a primary amino group and a couplercompound having the-formula:

where X is selected from the group consisting of CN and COOR: where Rais-alkyl, Z is selected from the group consisting of NHR1 and alkoxy R1and R2 are selected from the group consisting of H, alkyl and aryl, Y isselected from the group consisting of oxygen, sulfur and NR4, where R4is selected from the group consisting of H, alkyl and aryl.

2. A color forming photographic developer comprising an aromatic aminodeveloping compound containing a primary amino group and a couplercompound having the formula:

4 pound containing a primary amino group and cyanoacetyl guanidine. Y

. 4. A color forming photographic developer comprising an aromatic aminodeveloping compound containing a primary amino group and,

a coupler compound having the formula:

is selected from the group consisting of oxygen, sulfur and NR4, whereR; is selected from the group consisting of H, alkyl and aryl.

5. A color forming photographic developer comprising an aromatic aminodeveloping compound containing a primary amino group and ethyl malonylurea.

6. A color forming photographic developer comprising an aromatic aminodeveloping agent containing a primary amino group and a coupler compoundhaving the formula:

R; l lH( 3I lOOCHaCN where R1 and R2 are selected from the groupconsisting of H, alkyl and aryl, Y is selected from the group consistingof oxygen and sulfur.

'7. A color forming photographic developer comprising an aromatic aminodeveloping compound containing a primary amino group and cyanoacetylurea.

8. The method of producing a colored photographic image in a lightsensitive silver halide emulsion layer which comprises exposing thelayer and developing it with an aromatic amino developing compoundcontaining a primary amino group in the presence of a coupler compoundhaving the formula:

where X is selected from the group consisting of CN and COORa where R:is alkyl, Z is selected from the group consisting of NHR1 and alkoxy R1and R2 are selected from the group consisting of H, alkyl and aryl, Y isselected from the group consisting of oxygen, sulfur and NR4 where R4 isselected from the group consisting of H, alkyl and aryl.

9. The method of producing a colored photographic image in a lightsensitive silver halide emulsion layer which comprises exposing thelayer and developing it with an aromatic amino developing compoundcontaining a primary amino group in the presenceof a coupler compoundhaving the formula:

where R1, R2 and R4 are selected from the group consisting of H, alkyland aryl.

10. The method of producing a colored photographic image in a lightsensitive silver halide emulsion layer which comprises exposing thelayer and developing it with an aromatic amino developing compoundcontaining a primary amino group in the presence of cyanoacetylguanidine.

11. The method of producing a colored photographic image in a lightsensitive silver halide emulsion layer which comprises exposing thelayer and developing it with an aromatic amino developing compoundcontaining a primary amino group in the presence of a coupler compoundhaving the formula:

1 i 1 NH-i-N-CO-CHPCOOR where R is alkyl, and R1 and R2 are selectedfrom the group consisting of H, alkyl and aryl,

Y is selected from the group consisting of oxygen, sulfur and NR4, whereR4 is selected from the group consisting of H. alkyl and aryl.

12. The method of producing a colored photographic image in a lightsensitive silver halide emulsion layer which comprises exposing the.

layer and developing it with an aromatic amino developing compoundcontaining a primary amino group in the presence of ethyl malonyl urea.e

13. The method of producing a colored photo,- graphic image in a lightsensitive'silver halide emulsion layer which comprises exposing thelayer and developing it with-an aromatic amino developing compoundcontaining a primary amino group in the presence of a coupler com poundhaving the. formula;

i" i f NHCNCOCH:CN

where R1 and R2 are selected from the group consisting of H, alkyl andaryl, Y is selected from the group consisting of. oxygen and sulfur.

14. The method of producing a colored photoemulsion having incorporatedtherein a coupler compound having the formula:

' R1 NR4 R2 v where Rn-R2, and R4 are selected from the group consistingof H, alkvl and aryl, R4 is selected from the group consisting of H,alkyl and aryl.

17. A photographic emulsion for forming colored images comprising agelatino silver halide emulsion having incorporated therein cyanoacetylguanidine.

18. A photographic emulsion for forming colored images comprising agelatino silver halide emulsion having incorporated therein a couplercompound having the formula:

r i r NH-CN-C0CHz-CO0R where'R is alkyl, and R1 and-R's are selectedfrom the group consisting of H, alkyl and aryl,

graphic image in a light sensitive silver halide emulsion layer whichcomprises exposing the layer and developing it with an aromatioaminodeveloping compound containing a primary amino group in the presence ofcyanoacetyl urea.

15. Aphotographic emulsion for forming colored images comprising acarrier containing a sensitive silver halide and a coupler compoundhaving the formula:

where X is selected from the group consisting of CN and CQORa where R;is alkyl, 2 is selected from the group consisting of NHR1 and alkoxy R1and R2 are selected from the group consist-- ing of H, alkyl and aryl,-Yis selected from the group consisting of oxygen, sulfur and NR4 where R;is selected from the group consisting of H, alkyl and aryl. g

16. A photographic emulsion for forming colored images comprising agelatino silver halide Y is selected from the group consisting ofoxygen, sulfur and NR4, where Rr'is selected from the group consistingof H, alkyl' and aryl.

19. A photographic emulsion for forming colorcd images comprising agelatino silver halide emulsion having incorporated therein ethylemulsion having incorporated therein cyanoacetyl urea. CHARLES E. H.ALIEN.

PAUL W. V1'1I'UM'.-

